Water Air Soil Pollut (2017) 228:278

DOI 10.1007/s11270-017-3461-y

Synthesis of a Quaternized Beta

Cyclodextrin-Montmorillonite Composite and Its Adsorption
Capacity for Cr(VI), Methyl Orange, and p-Nitrophenol
Anrong Zeng & Anran Zeng

Received: 24 March 2017 / Accepted: 27 June 2017

# Springer International Publishing AG 2017

Abstract In this paper, quaternized β-cyclodextrin– process and could be spontaneous at given temperature
montmorillonite composite (QCD-MMT) was obtained range, except for Cr(VI), of which adsorption should be
and absorption properties of Cr(VI), methyl orange and at much higher temperature. Overall, QCD-MMT ex-
p-nitrophenol were studied. QCD was prepared by 2,3- hibited potential for practical applications in the treat-
epoxypropyltrimethylammonium chloride and β- ment of both metal ions and organic pollutants.
cyclodextrin (β-CD). QCD-MMT was obtained by re-
action between QCD and montmorillonite suspensions, Keywords Beta-Cyclodextrin . Montmorillonite .
which could be attributed to the montmorillonite cation Composite . Adsorption capacity
ion exchange properties. β-CD cavities of this compos-
ite were expected to capture organic molecules through
inclusion, while montmorillonite units acted as the ad-
1 Introduction
sorption sites for metals. QCD-MMT was characterized
by FT-IR, elemental analysis, XRD, SEM-EDX, and
With rapid development of industrialization and urban-
TGA. Adsorptions of Cr(VI), methyl orange, and p-
ization, a variety of hazardous molecules was used and
nitrophenol were highly dependent on adsorbent dose,
could be possibly discharged into the natural environ-
initial concentration, temperature, contact time, and pH.
ment. For example, synthetic dyes were commonly used
Adsorption kinetics of Cr(VI), methyl orange, and p-
in textile, cosmetics, and other industries (Yan et al.
nitrophenol followed the pseudo-second-order model.
2016). Dye containing wastewater could endanger hu-
Meanwhile, adsorption of Cr(VI) fit better in the
man health without effective treatment. Also, pollutants
Freundlich model, inferring a multilayer adsorption,
like p-nitrophenol has become one of the commonly
while the adsorption of methyl orange and p-
encountered pollutants in water pollution, and it could
nitrophenol fit better in Langmuir model, inferring a
be persistent, bio-accumulative, and highly toxic at very
monolayer adsorption. Thermodynamic analysis
low concentration (Shen et al. 2015). Moreover, metal-
showed that the adsorptions were all endothermic
bearing effluents originating from metal plating, mining
operations, nuclear power plant, and metallurgical and
A. Zeng (*) : A. Zeng
battery manufacturing industries, often contained many
College of Light–Textile Engineering, Liming Vocational kinds of heavy metal ions, such as lead, cobalt, nickel,
University, Quanzhou 362000, China cadmium, chromium, and mercury ions. Heavy metals
e-mail: anrongzeng@qq.com were non-biodegradable and can accumulate slowly in
A. Zeng : A. Zeng
the body of living creatures, causing various diseases
Applied Technology Center of Fujian Provincial Higher Education such as poisoning, nervous system damage, and cancer
for Practical Chemical Material, Quanzhou 362000, China (Vašák and Meloni, 2011; Zheng 2001). Overall, those
278 Page 2 of 17
pollutants could further lead to many serious environ-
mental problems, like water pollution and further seri-
ous public health issue. Therefore, effective treatments
are becoming more and more urgent.
A lot of water treatment methods have been reported.
For example, adsorption, ion exchange, and reverse
osmosis have been applied to the removal of chromium
and mercury in paper and textile industries (Liu et al.
2016). Oxidation, membrane separation, and extraction
were also developed to remove p-nitrophenol or its
analogues from wastewater (Shen et al. 2015). For dyes
containing wastewater treatment, methods like adsorp-
tion, oxidation process, precipitation, coagulation, and
electro-chemical treatment could be applied (Debnath
et al. 2017). Among these approaches, adsorption was
used most frequently. It was cost saving, efficient, and
promising to remove both organics and heavy metals
from wastewater (Chen et al. 2015; Debnath et al. 2017).
β-cyclodextrin (β-CD) has been found to be effective to
remove heavy metals (Liu et al. 2016). It is usually used
as a kind of pharmaceutical excipients. β-CD has a
torus-shaped cyclic oligosaccharide structure with abun-
dant hydroxyl groups on both ends, and a hydrophobic
cavity. As a result, it shows good ability to capture
organic molecules. However, the water-solubility of β-
CD limits its application to some extent, and it is im-
portant to improve its insolubility in water. One way
reported was to use cross-linkers to obtain β-CD poly-
mers. For example, EDTA-β-CD was employed in the
adsorption of aqueous dyes and metal ions (Zhao, Repo,
Meng, et al., 2015b; Zhao, Repo, Yin, et al., 2015a). The
enhanced metal adsorption ability of β-CD was attrib-
uted to EDTA’s functional groups of chelating metal
ions. Similar modifications were reported to improve
the chitosan’s metal ion affinities as well, by using
EGTA, EDTA, and DTPA (Zhao, Repo, Sillanpää,
et al., 2015c; Zhao et al. 2013). Another way to increase
β-CD insolubility was to prepare inorganic-organic
composite adsorbents, which has been applied to im-
prove certain polymer’s adsorption performance. For
instance, hydroxamic-acid-modified polyacrylamide/
Fe3O4 composite was prepared and showed affinity
towards Cd(II), Pb(II), Co(II), and Ni(II) (Zhao et al.
2014).
Montmorillonite (MMT), with an ideal molecular
formula of [Al2(Si4O10)(OH)2 ∙ XH2O], is present in a
type of hydrous, porous aluminum silicate layer mineral.
MMT mines are abundant in nature, and their price is
quite low. In terms of its cheapness and features (Li et al.
Water Air Soil Pollut (2017) 228:278
2014), it was widely used as an adsorbent for water
treatment, especially for heavy metal treatment.
In this work, we prepared a β-CD/MMT composite
(QCD-MMT) for adsorption of Cr(VI) ions (as the
representative of heavy metal ions), methyl orange (as
the representative of dye compounds), and p-
nitrophenol (as the representative of phenols pollutants),
in aqueous solution. In order to further investigate the
interaction between QCD-MMT and different adsor-
bates, the adsorption behavior was studied in terms of
various parameters such as adsorption kinetics, adsorp-
tion isotherms, and thermodynamic models.
2 Materials and Methods
2.1 Materials
β-CD was 96% pure and purchased from Aladdin. MMT
was purchased from Zhejiang Fenghong New Material
Co. Ltd., industrial grade; 2,3-epoxypropyltrimethyl am-
monium chloride (EPTAC) was purchased from Shang-
hai Dibo Chemical Co. Ltd., analytical grade. Other
reagents were purchased from Xilong Scientific, analyti-
cal grade. All reagents were used without further
purification.
Potassium dichromate, methyl orange, and p-
nitrophenol stock solutions were prepared via dissolving
in deionized water. Working solutions of metals and
dyes were prepared by diluting the stock solutions.
The three adsorbates properties were summarized in
Table 1.
2.2 Synthesis of QCD-MMT Composite
The synthetic process of QCD-MMT was shown in Fig.
1. β-CD was dissolved in NaOH solution (pH = 12) in a
flask equipped with a mechanical stirrer, thermometer,
reflux cooler, and drop funnel. EPTAC aqueous solution
(75% by weight) was added into the drop funnel and
further added dropwise into the flake. Mass ration of
EPTAC and β-CD was 80/20. The reaction was con-
ducted at 60 °C for 3 h. Then the reaction system was
cooled to room temperature to obtain QCD.
MMT was suspended in water with QCD. Mass ratio
of MMT and β-CD was of 10/1. The reaction was
further conducted for another 24 h while sufficiently
stirring at room temperature. The pH was adjusted to
neutral with hydrochloric acid solution. The solid was
Water Air Soil Pollut (2017) 228:278
Table 1 Adsorbates used in this paper
Adsorbates Chemical Formula
Potassium dichromate K2Cr2O7
Methyl orange
p-nitrophenol
further purified with deionized water, followed by dry-
ing in a vacuum oven of 60 °C. The final product was
QCD-MMT composite.
2.3 Characterization of QCD-MMT Composite
β-CD, MMT, and QCD-MMT FT-IR spectra were obtain-
ed using Bio-Rad FTS 6000 spectrometer. All samples
were prepared as KBr pellets. Elemental analysis was
determined using an Elementar Vario EL Cube analyzer,
CHN mode. X-Ray diffraction (XRD) data of MMT and
QCD-MMT power samples were performed with Bruker
powder X-ray diffractometer D8 Advance, with scan range
from 5° to 90° (2θ). The surface morphology and energy-
dispersive X-ray (EDX) spectroscopy were performed by
field emission scanning electron microscopy (FE-SEM,
Hitachi S4800). Thermogravimetric analysis (TGA) was
also conducted on a TA instrument Q500 to assess QCD-
Fig. 1 Synthesis of QCD-MMT
composite
Page 3 of 17 278
MMT’s thermal stability and organic content. Samples
were heated to 800 °C at a heating rate of 10 °C/min in a
nitrogen flow of 40 ml/min.
The organic content was calculated as the percentage of
organic mass with respect to the dried mass of MMT. The
dried mass of initial mass was obtained at 200 °C from
thermogravimetric curves in order to avoid the contribu-
tion of water, which could introduce error if samples were
not dried correctly. The mass of organic compounds was
calculated from the mass loss registered between 200 and
800 °C, so the organic content would be calculated as
following Eq. (1) (Ezquerro et al. 2015):
 
mi −m f
Orangic content ¼  100 −%ΔmMMT ð1Þ
mi
where mi and mf were the mass of QCD-MMT at 200 and
800 °C, respectively; %ΔmMMT was the mass loss
278 Page 4 of 17
observed in the same region of temperature for the unmod-
ified sample. The decomposition of organics took place in
the range of 200 to 500 °C. The final temperature was
chosen at 800 °C, since some overlap with the
dihydroxylation of silicate layers was observed at around
500 °C.
The ratio of quaternary ammonium groups of QCD-
MMT was determined by N element ratio from element
analysis, compared with the results of Cl element per-
centage from EDX.
2.4 Adsorption Experiments
2.4.1 Adsorption Parameters’ Impact on QCD-MMT’s
Adsorption Performance
All adsorption experiments were undertaken by mixing
adsorbents with 30 mL potassium dichromate, methyl
orange, and p-nitrophenol solutions of different initial
mass concentrations. The impacts of usage, initial con-
centration, temperature, contact time, and pH were
determined.
For each adsorption system, the residual in the reac-
tion mixture was analyzed by centrifuging the reaction
mixture, and then measuring the absorbance of the
supernatant at the wavelength corresponding to the
maximum absorbance of the sample. Concentrations in
the reaction mixture were calculated from the calibration
curve. Methyl orange and p-nitrophenol concentrations
were determined by UV-vis spectrometry (T6 model,
Beijing Purkinje General Instrument Co., Ltd.) at the
maximum absorbance of dyes. Metal concentrations
were analyzed by an atomic absorption spectroscopy
(A3 model, Beijing Purkinje General Instrument Co.,
Ltd.).
The amount of adsorbate adsorbed onto QCD-MMT,
qe (mg/g), was calculated by the following mass balance
relationship:
V The Langmuir model is valid for monolayer adsorp-
qe ¼ ðC 0 −C e Þ ð2Þ
W tion onto a surface with a finite number of identical sites.
where C0 and Ce were initial and equilibrium liquid-
phase concentration of waste, respectively (mg/L), V
was the volume of the solution (L), and W was the
weight of the QCD-MMT used (g).
Water Air Soil Pollut (2017) 228:278
2.4.2 Adsorption Kinetics Analysis
To determine QCD-MMT’s adsorption kinetics of
Cr(VI), methyl orange and p-nitrophenol, independent
bottles containing 30 mL samples and 0.05 g QCD-
MMT, were used to get accurate results for each point
on the graph. The initial concentration of potassium
dichromate solution, methyl orange solution and p-
nitrophenol solution was 360, 250, and 25 mg/L, re-
spectively. Adsorption experiments’ contact time varied
from 15 to 180 min. Adsorption was carried out at the
temperature of 30 °C.
In order to investigate the adsorption mechanism of
three different adsorbates, two commonly used reaction
kinetic models viz., pseudo-first-order and pseudo-
second-order models were used (Xing and Wang
2016). The kinetic data were utilized to investigate the
suitability of these models. The linear equations of
pseudo-first-order and pseudo-second-order models
were expressed as Eqs. (3) and (4), respectively:
qt ¼ qe1 −qe1 e−k 1 t ð3Þ
t t 1
¼ þ ð4Þ
qt qe k 2 qe 2
In Eq. (3), qe1 and qt were the adsorption capacity at
equilibrium and at time t, respectively (mg/g); k1 was the
rate constant of pseudo-first-order model (min−1). In Eq.
(4), qe2 and qt were the adsorption capacity at equilibri-
um and at time t; k2 (slope2/intercept) was the pseudo-
second-order rate constant (g/mg/min).
2.4.3 Adsorption Isotherms Analysis
Isothermal studies were conducted with QCD-MMT
usage of 0.05 g and 30 mL adsorbates solutions by
shaking the reaction mixture for equilibrium time. The
adsorption temperature was of 303.15, 313.15, and
323.15 K, respectively.
The Langmuir equation was as follows (Xing and
Wang, 2016):
qm K L C e
qe ¼ ð5Þ
1 þ K L Ce
where Ce and qe were equilibrium concentration (mg/L)
Water Air Soil Pollut (2017) 228:278
and the amount of adsorbates adsorbed on QCD-MMT
(mg/g), respectively. The constant KL was related to the
energy of adsorption and the constant qm represents the
maximum amount of adsorbates absorbed per unit
weight of QCD-MMT.
The Freundlich model can be applied to non-ideal
sorption on heterogeneous surfaces as well as multilayer
sorption and was expressed by the following equation
(Xing and Wang, 2016):
1
qe ¼ K F C en ð6Þ
where KF and n were the Freundlich constants. KF and n
are indicators of adsorption capacity and adsorption
intensity of the QCD-MMT, respectively.
2.4.4 Adsorption Thermodynamics Analysis
The thermodynamic parameters (ΔH , ΔS , and ΔG )
0 0 0
for three different adsorbates onto QCD-MMT can be
calculated from the temperature-dependent adsorption
isotherms. The equation was as follows (Li et al. 2013;
Xing and Wang, 2016):
ΔS 0 ΔH 0
lnK 0 ¼ − ð7Þ
R RT
where R is the universal gas constant (8.314 kJ/(mol
K)); T is the temperature in Kelvin; K0 is the adsorption
equilibrium constant and can be calculated by plotting ln
Kd versus Ce and extrapolating Ce to zero, where Kd was
defined as qe divided by Ce.
3 Results and Discussion
3.1 Characterizations of QCD-MMT
3.1.1 FT-IR Spectroscopy
Figure 2 showed the FT-IR spectra of raw β-CD,
raw MMT, and QCD-MMT composite. Compared
with MMT, the peaks at 2928 cm−1 of QCD-MMT
could be attributed to the methyl groups’ asym-
metric stretching vibration (Zhao et al. 2009). The
peaks at 1487 cm−1 of QCD-MMT indicated the
existence of −CH2-N+, compared to β-CD, and
could be assigned to NH3+. Besides, a characteris-
tic absorption peak of α-type glycosidic bond was
found at 855 cm−1 of QCD-MMT, which indicates
Page 5 of 17 278
that β-CD was formed by glucopyranose units
through α-1,4-glycosidic bond (Yuan et al. 2015).
The peak of 1414 cm−1 was one of the typical
peaks corresponding to the deformation vibration
of the O-H bonds in the primary and secondary
hydroxy groups of β-CD, and also C-H bending
vibrations (Zhao et al. 2009). It could be inferred
that the structure characteristics of β-CD were
maintained. Moreover, compared MMT with
QCD-MMT, the peaks at 521 and 465 cm−1 could
be attributed to the Si-O-Al stretching vibration
and Si-O bending vibration. Therefore, it could
be concluded that the modification of β-CD and
MMT was successful.
3.1.2 Element Analysis
The results of quantitative elemental analysis were
presented in Table 2. Data showed the C and N
element content of QCD-MMT was increased. The
calculated quaternary ammonium group percentage
was 8.22 wt.% basing on N element content. This
proved the final product was quaternized success-
fully. This inference was echoed by EDX. EDX-Cl
element content was also given in Table 2, and the
calculated quaternary ammonium group percentage
was 13.02 wt.%. EDX spectrum was recorded to
identify the expected compositions on a selected
rectangle area of MMT and QCD-MMT sediment.
The difference between two results might be ex-
plained by uneven quaternary ammonium group
distribution. There might be more quaternary am-
monium groups on QCD-MMT’s surface. In this
paper, results based on element analysis were de-
termined as the quaternary ammonium group
percentages.
3.1.3 X ray Diffraction (XRD)
Figure 3 displayed the XRD pattern of raw MMT and
QCD-MMT. It showed that raw MMT has a d (001)-
spacing of 1.335 nm, basing on Bragg Eq.
(2)d001sinθ = λ (λ = 0.154 nm) calculation. After mod-
ification, the QCD-MMT’s d001-spacing was enlarged to
1.409 nm. It could be inferred that the modification may
occur in the MMT interlayer. This might also benefit
QCD-MMT’s adsorption capacity.
278 Page 6 of 17 Water Air Soil Pollut (2017) 228:278

Fig. 2 FT-IR spectra of MMT, β-

CD, and QCD-MMT

3.1.4 SEM-EDX Analysis identify the expected composition on a selected

SEM provided information about morphology changes
before and after modification. Images were collected in
Fig. 4a, b. In the pristine state, MMT showed a rough
surface where large lamellas were observed. QCD-
MMT’s surface was smooth after modifications with
QCD.
Simultaneously to SEM images, EDX spectros-
copy analysis was also carried out to determine the
quaternary ammonium amount. Results were
shown in Fig. 5 and Table 3. Cl element content
was increased from 0.09 wt.% to 3.14 wt.%. Cl
ion was the counter ion of quaternary ammonium
in QCD-MMT and indicated that the MMT had
been quaternized successfully (Rosa et al. 2008;
Sowmya and Meenakshi, 2013; Yao et al. 2014).
However, since EDX only analyzes the surface and
rectangle area, we took EDX as supplement data
for element analysis.
3.1.5 Thermogravimetric Analysis
TGA and derivative thermogravimetric (DTG)
curves were shown in Figs. 6 and 7, respectively,
and were also summarized in Table 4. The DTG
curves provided information about different steps
of decompositions. The thermal decomposition of
MMT could be divided into four different regions
(Ezquerro et al. 2015; Xie et al. 2014). The first
weight loss region was desorption of water and
physisorbed species, which happened below
180 °C. The second region was located in the
range from 200 to 500 °C and involves the de-
composition of organic species. The third region

Table 2 MMT and QCD-MMT element analysis

Sample Element content (wt.%) Total quaternary ammonium group wt.% Quaternary ammonium group wt.% (EDX result)

N C H

MMT 0.56 0.95 1.827 / /

QCD-MMT 1.32 11.19 2.709 8.22a 13.02b
a
Calculated from nitrogen content of element analysis: quaternary ammonium group wt.% = (1.32–0.56)/MN * MEPTAC, where MN stands
for molar mass of N element, MEPTAC stands for molar mass of EPTAC
b
Calculated from chlorine content of EDX analysis: quaternary ammonium group wt.% = (3.14–0.09)/MCl * MEPTAC,xxx where MCl stands
for molar mass of Cl element, MEPTAC stands for molar mass of EPTAC
Water Air Soil Pollut (2017) 228:278
Fig. 3 XRD patterns of MMT
and QCD-MMT
was from 500 to 700 °C, when aluminosilicate
layers’ dehydroxylation took place. Finally, in the
last step between 700 and 1000 °C, the evolution
of products associated with organic carbonaceous
residue occurs.
The position of these steps in the derivative
mass curves is referred as the temperature of max-
imum decomposition rate in Table 4 (T1, T2, and
T3). T1 corresponds to desorption of water and
other physisorbed species, T2 refers to the decom-
position step of organic species, and T3 refers to
the aluminosilicate layers’ dihydroxylation. The
decomposition of carbonaceous residue was not
registered in the curves below the maximum tested
temperature of 800 °C.
DTG of MMT showed only two peaks (T1 and
T3). The first one was below 100 °C (T1), and the
mass loss was associated to the evaporation of
water adsorbed. The second decomposition step
occurred in the range 550–750 °C (T3) and could
be attributed to the dihydroxylation of the layer
crystal lattice. QCD-MMT showed one additional
peak at around 304 °C, which was associated to
the decomposition of organic compound introduced
to MMT.
Organic content of QCD-MMT was calculated
basing on TGA result, which was 16.25 wt.%.
Considering element analysis results, CD content
was around 8.03 wt.%, while QCD content was
Page 7 of 17 278
around 9.10 wt%. Those results were also given in
Table 4.
3.2 Cr(VI), Methyl Orange and p-Nitrophenol
Adsorption Experiments
3.2.1 Influence of QCD-MMT Usage
The influence of adsorbent usage was studied, and
the results were shown in Fig. 8, where qe represent-
ed the sorption amount of Cr(VI), methyl orange and
p-nitrophenol on QCD-MMT (mg/g) in equilibrium
time. At the usage of 0.05 g, the adsorption capacity
for Cr(VI), methyl orange, and p-nitrophenol was
51.98, 25.00, and 24.56 mg/g, respectively. Adding
more adsorbent will decrease the adsorption capacity.
It could be also noticed that the difference between
initial concentration and Ce did not fluctuate a lot (Ce
values of Cr(VI), methyl orange, and p-nitrophenol
shown in Fig. 8). This could be explained by that the
adsorption was driven by adsorbates’ concentration
gradient (Xing and Wang, 2016). Given that concen-
tration gradients in each adsorption were similar and
the total adsorbates adsorbed did not change a lot, the
adsorption capacity would be decreased when QCD-
MMT usage increased. Also, the aggregation and
competition of QCD-MMT adsorbent might also
have impacts the adsorption behaviors.
278 Page 8 of 17
Fig. 4 SEM images of MMT (a) and QCD-MMT (b)
3.2.2 Influence of Initial Concentration
Figure 9 showed the influence of the initial concen-
trations on QCD-MMT’s sorption levels, respec-
tively. The adsorption capacities of Cr(VI) in-
creased as the initial concentrations increased.
Methyl orange and p-nitrophenol showed similar
trends. When the initial methyl orange concentra-
tion was up to 250 mg/L at different temperatures
of 30, 40 and 50 °C, the adsorption capacity was
53.217, 58.784, and 64.881 mg/g, respectively. For
p-nitrophenol, when the initial concentration was
increased, the adsorption capacity was largely en-
hanced. The maximum adsorption was 51.212 mg/
Water Air Soil Pollut (2017) 228:278
g at 50 °C, of which initial concentration was
200 mg/L. The increasing initial p-nitrophenol
concentrations could not always increase adsorp-
tion. On the contrary, the adsorption was slightly
lower. It was possible that high concentrations
resulted in competition between p-nitrophenol and
then slowed down the adsorption. Also, high con-
centration of p-nitrophenol might occupy and
block the QCD-MMT inclusion sites at the sur-
face, preventing further p-nitrophenol dispersion.
3.2.3 Influence of Contact Time
In order to determine the adsorption equilibration
time of different adsorbates and also to investigate
the kinetics of adsorption process, the adsorption
capacity as a function of contact time was studied.
Three different samples showed similar trends.
As adsorption time changed from 15 to 180 min,
the adsorption capacity first increased steadily then
afterwards no significant change observed. For
Cr(VI) and methyl orange, near equilibrium was
achieved in around 1.5 h, while for p-nitrophenol
in around 2.5 h. This was probably due to larger
surface area of QCD-MMT being available at the
beginning for adsorptions. As time progressed, the
surface coverage of the adsorbent was high and
then no adsorption took place. Figure 10a–c
showed the effect of time on adsorption. The equi-
librium adsorption capacities of Cr(VI), methyl
orange, and p-nitrophenol were around 43, 50,
and 6.5 mg/g, respectively.
3.2.4 Influence of pH
Impact of pH was shown in Fig. 11. The adsorp-
tion capacities of Cr(VI) at different pH environ-
ment ranged from 34.80 to 51.98 mg/g. The ad-
sorption capacities were higher at acidic and neu-
tral condition. Maximum adsorption capacity of
Cr(VI) reached the maximum at pH of 7. At lower
pH, HCrO4− was the major form of Cr(VI). It is
possible that the quaternary ammonium groups on
the adsorbents were easily protonated and positive-
ly charged, which facilitated the approach of the
negatively charged HCrO4− due to the electrostatic
interaction (Liu et al. 2016). Also, at lower pH,
the counter anion Cl− of quaternary ammonium
groups might be displaced by HCrO 4 − (Wang
Water Air Soil Pollut (2017) 228:278 Page 9 of 17 278

Fig. 5 SEM-EDX spectrum of MMT (a, b) and QCD-MMT (c, d) sediments

et al. 2016). Moreover, a probable mechanism was sites than −OH. The ion exchange could take place
proposed to be ion exchange between chromium through the following reactions (Wang et al.
and surface −OH groups or hydroxide groups of 2016):
Al polycations proceeded in the interlayer spaces.
≡S−OH− þ Hþ →≡S−OHþ
At lower pH, −OH groups were protonized to 2

−OH2+, which facilitates the ligand exchange since

–OH2+ is easier to displace from metal binding
≡S−OH− þ HCrO−4 →≡S−HCrO−4 þ OH−
Table 3 Composition of MMT and QCD-MMT determined by
SEM-EDX
≡S−OHþ − −
2 þ HCrO4 →≡S−HCrO4 þ H2 O
Element MMT QCD-MMT

Wt.% At.% Wt.% At.%

For methyl orange, the adsorption capacities
CK 02.69 04.73 10.27 17.23 changed from 12.43 to 23.72 mg/g at different pH
OK 39.16 51.67 36.19 45.58 values. With pH value of 3 ~ 11, the adsorption
NaK 02.70 02.48 01.66 01.45 capacities were around 22 mg/g without significant
MgK 02.91 02.53 02.39 01.98 changes. The hydroxyl of QCD-MMT might form
AlK 10.98 08.59 09.26 06.92 hydrogen bonds with N atoms of methyl orange
SiK 35.72 26.85 30.48 21.86
skeleton. Meanwhile, hydroxyl proton can produce
ClK 00.09 00.05 03.14 01.78
electrostatic adsorption with SO3− contained in MO
molecules (Yan et al. 2016). Moreover, the inclusion
278 Page 10 of 17
Fig. 6 TGA curves of MMT and
QCD-MMT
between methyl orange and β-CD unit of QCD-
MMT also benefit adsorption. When pH was of 13,
the hydrogen bonds might not be easy to form be-
tween β-CD unit and methyl orange, since the OH−
in the solution would compete with methyl orange
and form hydrogen bonds with β-CD unit. This
would further decrease electrostatic adsorption and
then inclusion, resulting in lower adsorption (Yan
et al. 2016).
For p-nitrophenol, the maximum adsorption was
obtained at pH of 5, which was 21.45 mg/g. Also,
at pH of 11, the adsorption was high (19.36 mg/g)
as well. The fluctuation could be explained by the
Fig. 7 DTA curves of MMT and
QCD-MMT
Water Air Soil Pollut (2017) 228:278
combination of host-guest inclusion, electrostatic
repulsion, and hydrogen bond interaction (Li
et al. 2011; Shen et al. 2015). When pH was
low, both β-CD unit and p-nitrophenol become
protonated, so p-nitrophenol cannot be adsorbed
on β-CD efficiently for the electrostatic repulsion
between them. This results in lower adsorption
capacity at pH of 1 and 3. When pH value in-
creased, protonation of β-CD and p-nitrophenol
became weak. This might benefit the host-guest
inclusion between them, and reach the maximum
adsorption at pH of 5. As the pH became higher
(pHs of 7 and 9), inclining adsorption was
Water Air Soil Pollut (2017) 228:278 Page 11 of 17 278

Table 4 TGA-DTG results of MMT and QCD-MMT

Sample Temperature of Residue at 800 °C Organic content CD content QCD content Total EPTAC content
maximum (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
decomposition
rate (°C)

T1 T2 T3

MMT 64 – 661 85.08 / / / /

QCD- 60 304 635 75.69 16.25a 8.03b 9.10b 8.22b
MMT 92
a
Organic content calculated from Eq. (1)
b
CD content calculated from following equations:
MQCD * nQCD + MEPTAC * nEPTAC = organic content
nQCD + nEPTAC = mN / MN
nQCD = nCD
where MQCD stands for molar mass of QCD, MEPTAC stands for molar mass of EPTAC, nQCD stands for mole number of QCD, nEPTAC stands
for mole number of EPTAC, mN stands for mass of N element, and MN stands for molar mass of N element

observe. When the pH reached pH of 11, the adsorption capacity could be attributed to host-
alkaline environment greatly weakened the proton- guest inclusion and hydrogen bond interaction.
ation of β-CD and p-nitrophenol, so the increased However, when the pH was of 13, certain amount

Fig. 8 Influence of usage on QCD-MMT adsorption capacity and

adsorbates’ equilibrium concentration (contact time 24 h; initial Fig. 9 Influence of adsorbates’ initial concentrations on adsorp-
concentration Cr(VI) 120 mg/L, methyl orange 50 mg/L, p- tion capacity on different temperatures (contact time 24 h; QCD-
nitrophenol 50 mg/L; temperature 30 °C; neutral) MMT usage 0.05 g; neutral)
278 Page 12 of 17
Fig. 10 1 QCD-MMT’s adsorption capacity was plotted as a
function of time. Adsorption kinetics was investigated using 2
pseudo-first-order and 3 pseudo-second-order models. a Cr(VI),
QCD-MMT 0.05 g, 30 °C, neutral, initial concentration 120 mg/L.
of p-nitrophenol might form p-nitrophenol sodium
salt with sodium hydroxide. The hydrophobic in-
clusion could be impacted, causing decreasing
adsorption.
Overall, the adsorption was pH dependent. More
investigation would be conducted in the future to ex-
plore more details about the mechanism.
3.3 Adsorption Kinetics
Pseudo-first-order and pseudo-second-order models
were used to evaluate the sorption kinetic. The ki-
netic parameters for adsorption of three different
samples were given in Table 5. For all three sam-
ples, the pseudo-second-order equation fitted better
Water Air Soil Pollut (2017) 228:278
b Methyl orange, QCD-MMT 0.05 g, 30 °C, neutral, initial con-
centration 250 mg/L. c p-Nitrophenol, QCD-MMT 0.05 g, 30 °C,
neutral, initial concentration 25 mg/L
for the data, considering higher R2 and higher agree-
ment between the calculated and experimental qe
values. This explained chemisorption controls the
rate of adsorption. Table 5 and Fig. 12 showed the
detailed values. In chemisorption, the adsorbate ad-
hered on QCD-MMT by formation of a chemical
bond, and also searched for adsorption sites. This
would maximize their coordination number with the
surface (Kumar and Kirthika, 2009; Mishra et al.
2017). Furthermore, the kinetics of p-nitrophenol
and methyl orange was faster than that of Cr(VI),
suggesting that the β-CD cavities inclusion process
was faster than MMT complexing, comparing
pseudo-second-order rate constant k2 values (Zhao,
Repo, Yin, et al., 2015a).
Water Air Soil Pollut (2017) 228:278 Page 13 of 17 278

monolayer coverage of methyl orange or p-

Fig. 11 Influence of pH on QCD-MMT adsorption capacity and
adsorbates’ equilibrium concentration (contact time 24 h; initial
concentration Cr(VI) 120 mg/L, methyl orange 50 mg/L, p-
nitrophenol 50 mg/L; temperature 30 °C; neutral)
3.4 Adsorption Isotherms
As shown in Fig. 12 and Table 6, the Langmuir
isotherm model provides the better fit for the
methyl orange and p-nitrophenol equilibrium data.
This suggested that the adsorption for methyl or-
ange and p-nitrophenol was monolayer, or homo-
geneous adsorption (Debnath et al. 2017). Each
methyl orange or p-nitrophenol molecule might
have equal adsorption affinity towards QCD-
MMT (Shen et al. 2015). It was possible that the
nitrophenol molecule was formed at the outer sur-
face of QCD-MMT (Malik 2004). Since β-CD was
the effective component for organic methyl orange
and p-nitrophenol, it would be inferred that the β-
CD distributed homogenously at the final QCD-
MMT composite. Debnath et al. reported the sim-
ilar observation (Debnath et al. 2017). They used
β-CD modified pinecone to remove safranine O,
brilliant green, and methylene blue; the adsorption
also followed the Langmuir isotherm.
The introduction of β-CD to the QCD-MMT com-
posite enabled the cavity structure to capture organic
molecules. It may be inferred that the interactions be-
tween the organic molecules used in this article and the
β-CD were primarily due to host-guest inclusion. Also,
methyl orange and p-nitrophenol molecules might have
possible hydrogen bonding with the hydroxyl groups on
the surface of the β-CD.
Cr(VI) adsorption fits Freundlich isotherm mod-
el better, suggesting a multilayer adsorption for
Cr(VI). This result could be attributable to the
large montmorillonite spacing and the cationic ad-
sorption sites for Cr(VI) due to surfactant loadings.
These cationic adsorption sites might be favorable
to the Cr(VI) adsorption through anion exchange
between the counter anion of surfactant and
HCrO 4 − or Cr 2 O 7 2− (Wang et al. 2016). The
Cr(VI) adsorption on QCD-MMT might also
depended on electrostatic attraction and the ion
exchange between chromium and surface −OH
groups (Li et al. 2014). Also, the value of n from
Freundlich isotherm model was found to be slight-
ly higher than 1, which means that the adsorption
for Cr(VI) was a linear sorption.

Table 5 Adsorption kinetics of methyl orange on QCD-MMT

Kinetic models Equation Adsorbates Parameters

k Experimental Calculated R2
qe (mg/g) qe (mg/g)

Pseudo-first order qt ¼ qe1 −qe1 e−k 1 t Cr(VI) 0.068 43.000 41.943 0.8819
Methyl orange 0.072 50.000 48.227 0.8675
p-Nitrophenol 0.045 6.500 6.091 0.8318
Pseudo-second order t
qt ¼ qt þ k 21q2 Cr(VI) 0.002 43.000 45.558 0.9992
e2 e2
Methyl orange 0.004 50.000 49.383 0.9884
p-Nitrophenol 0.007 6.500 7.136 0.9931
278 Page 14 of 17 Water Air Soil Pollut (2017) 228:278

Fig. 12 Adsorption isotherm on QCD-MMT using L Langmuir and F Freundlich isotherm model. (The solid line represented the fit curves.
Neutral solutions; QCD-MMT usage of 0.05 g; contact time of 24 h a Cr(VI); b methyl orange; c p-nitrophenol)

3.5 Adsorption Thermodynamics 4 Conclusions

As shown in Table 7, for all three adsorbates, the posi-
tive standard enthalpy change ΔH0 values indicated that
the adsorption was endothermic process. The negative
standard free energy change ΔG0 values and positive
standard entropy change ΔS0 values indicated that the
adsorption process was spontaneous with high affinity.
ΔG0 values decreased with the increasing temperature,
implying more efficient adsorption at higher tempera-
tures. For Cr(VI) adsorption, the ΔG0 values became
negative when temperature was higher, around 50 °C.
In this paper, the adsorption capacities of QCD-MMT
composite towards Cr(VI), methyl orange, and p-
nitrophenol were studied. The adsorption capacities
might be attributed both to the hydrophobic cavity of
β-CD and the special metal-removing capacities of
MMT.
β-CD was cyclic oligosaccharides including glucose
units linked by α-1,4-glucosidic bonds (Zhang et al.
2013), which has a hydrophobic inner cavity and a
hydrophilic exterior (Qiao et al. 2010). This special
Water Air Soil Pollut (2017) 228:278 Page 15 of 17 278

Table 6 Isotherm parameter for adsorption of Cr(VI), methyl orange, and p-nitrophenol on QCD-MMT

Temperature Langmuir Freundlich

R2 qmax KL R2 KF n
K mg/g L/mg (mg/g)(mg/L)n

Cr(VI) 303.15 0.096 980.39 0.001 0.991 0.98 1.038

313.15 0.426 423.73 0.002 0.976 1.19 1.079
323.15 0.963 159.24 0.007 0.981 1.93 1.319
Methyl orange 303.15 0.994 75.47 0.016 0.963 2.59 1.597
313.15 0.995 87.11 0.866 0.978 2.44 1.526
323.15 0.988 102.77 0.011 0.99 2.39 1.468
p-Nitrophenol 303.15 0.988 44.05 0.126 0.73 8.74 2.927
313.15 0.986 47.12 0.109 0.814 8.84 2.849
323.15 0.979 50.15 0.105 0.811 9.00 2.773

cavity structure of β-CD constituted a kind of non-polar
micro-environment, allowing a number of small object
organic molecules and inorganic ions to enter. It could
package multiple object molecules to form supramolec-
ular complexes. The adsorption of methyl orange and p-
nitrophenol in this study could be ascribed to the inclu-
sion in the hydrophobic cavity of β-CD and hydrogen
bond interaction (Badruddoza et al. 2013; Shen et al.
2015). The kinetics study also showed that p-
nitrophenol and methyl orange adsorption followed
pseudo-second-order model and was faster than that
of Cr(VI), suggesting that the β-CD cavities inclu-
sion process was faster than MMT complexing
(Zhao, Repo, Yin, et al., 2015a). Moreover, the
isotherms fitting results of methyl orange and p-
nitrophenol adsorption indicated that the absorption
of these two molecules were better described by
Langmuir model, which was monolayer, or
homogeneous.
The composite also utilized MMT’s significant
adsorption capacities towards metal ions. This study
used Cr(VI) as a representative. The adsorption of
Cr(VI) was highly dependent on adsorbent dose,
initial concentration, temperature, and contact time.
The adsorption kinetics of QCD-MMT followed the
pseudo-second-order model. Adsorption of Cr(VI)
also fits better in the Freundlich model, inferring a
multilayer adsorption.
Thermodynamic analysis showed that the adsorp-
tion was all endothermic process and could be spon-
taneous at given temperature range, except for
Cr(VI), of which adsorption should be at much
higher temperature.
Further studies would be focused more on the
adsorption towards mixed wastewater containing
different types of pollutants. More detailed inves-
tigation into adsorption mechanism would be con-
ducted as well.

Table 7 Thermodynamic parameters of Cr(VI), methyl orange, and p-nitrophenol adsorption

Adsorbates ΔH0, kJ/mol ΔS0, J/(mol k) ΔG0, kJ/mol ΔG0, kJ/mol ΔG0, kJ/mol
303.16 K 313.16 K 323.16 K

Cr(VI) 5.38 17.03 0.22 0.05 −0.12

Methyl orange 2.48 8.43 −0.08 −0.16 −0.24
p-Nitrophenol 4.71 21.83 −1.90 −2.12 −2.34
278 Page 16 of 17
Acknowledgements The Science Foundations from the Depart-
ment of Education, Fujian Province (JA14428) and from Liming
Vocation University (LZ2016109) were acknowledged.
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